Catalytic oxidation of ammonia

ABSTRACT

This invention relates to the catalytic oxidation of ammonia. The catalytic compounds are complex catalysts with limited porosities, with specific surface areas between 0.02 and 2 m2/g, containing an active material bonded by ceramic-type bonds to the elements of a refractory carrier made of refractory oxides such as magnesia, zirconia, silica. 
     Such compounds are suitable for the oxidation of ammonia over fixed beds or fluidized beds.

This is a continuation, of application Ser. No. 112,879, filed Feb. 5, 1971.

This invention relates to the catalytic oxidation of ammonia to nitrogen oxides, notably nitrogen monoxide, for the production of nitric acid. The nitric acid industry habitually uses a catalyst made of pure platinum, or of mixtures of pure metals of the platinum group, as gauzes with wire thicknesses between a few hundredths and a few tenths of a millimeter.

It is well known that in the low-temperature range, selectivity must intervene to favor the formation of NO and NO₂ rather than N₂, while in the high-temperature range, selectivity must intervene to favor the formation of NO rather than N₂ O and N₂.

When using the known catalytic technique, the difficulty is to vary the selectivity, owing to the use of a catalyst with a very low thickness (thickness of the gauzes). For instance, with a reactor of 3 m diameter working at low pressure, the total thickness of the gauzes varies between a fraction of a millimeter and a few millimeters.

Besides, metal gauzes catalysts start losing their activity in a comparatively short time. The replacement, repair and regeneration of conventional catalyst involve costly down-time.

It has also been suggested that a catalytic metal or alloy of metals of the platinum group be deposited as a thin, continuous or quasi-continuous layer upon the surface of the flow ducts and the surface macropores of a porous and inert refractory structure.

Depositing a thin layer does not avoid the disadvantages due to lack of selectivity.

On the other hand, the dispersion and the structure of the active material, the nature of the carrier and its intimate bonding with the said active material, the promotors and the porosity have been found to be important factors for catalysis. Such factors cannot be varied, nor introduced simultaneously into a metal or a catalytic metal alloy.

According to this invention, selective catalytic compounds have been discovered which are thermally, mechanically and structurally stable, and which have high hardness and resist attrition.

The novel catalytic compounds have such thermal stability that their use at high temperatures (800°-1000°C) is possible without change of structure or loss of mechanical strength.

At low temperatures (500°-300°C), the catalytic compounds show high hardness and resist attrition, which allows their preferential use in fluidized beds with outstanding results.

The novel catalytic compounds according to the invention have a special structure of the crystals' unit cells which contains a great number of oxygen atoms, thus giving them special properties as catalysts.

On the other hand, the catalytic compounds according to the invention also have the advantage of making it possible to treat much larger flow rates of ammonia, with the same amount of active material, than with conventional platinum gauzes. The flow rates can be about 12 times larger than the usual ones. Moreover, the temperatures of treatment is about 100°C lower than with platinum gauzes.

The novel catalytic compounds make it possible to use very high volume rates, notably with stationary beds, while effecting the oxidation reaction within a very wide range of pressures, with satisfactory yields at high pressures.

The catalytic compounds of the invention are complex catalysts with limited porosities and specific surface areas between 0.02 and 2 m² /g containing an active material bonded by ceramic-type bonds to the elements of a refractory carrier made of refractory oxides, such as magnesia, silica and zirconia.

According to one embodiment of the invention, the active material of the said complex catalysts is a metal of the platinum group, in amounts between 0.1 and 10 %, preferably between 0.5 % and 4 %.

According to a favorable variation of the invention, the metal of the platinum group is associated with metal oxides or promoters such as the oxides of iron, nickel, cobalt, titanium, vanadium, bismuth and molybdenum.

It has been found that the use as promoters of metal oxides, notably of magnetite Fe₃ O₄, of vanadium pentoxide V₂ O₅, of cobalt oxide CoO, of nickel oxide NiO, bismuth oxide and hematite Fe₂ O₃ gives a special structure of the unit cell which contains a great number of oxygen atoms, and presumably has a favorable catalytic effect on the oxidation reaction.

The catalytic compounds in which the active material, in small amounts, is very intimately combined with the remainder of the carrier, mainly by ceramic-type bonds, may contain no platinum or metals of the platinum group. In such compounds the active material is made of one or several metal oxides known as promotes bonded by ceramic bonds to the refractory carrier.

According to the invention, such promoters, introduced separately or simultaneously and possibly alloyed to the metal of the platinum group, have the following contents in the compounds:

The content of Fe₃ O₄ is 0.5 % to 20 %, preferably 2 %.

The content of Fe₂ O₃ is 9 % to 80 %, preferably 9 to 65 %.

The content of V₂ O₅ is 0.5 % to 10 %, preferably 0.9 %.

The content of NiO is 4 % to 20 %, preferably 8 %.

The content of CoO is 4 % to 20 %, preferably 12 %.

The content of bismuth oxide is 4 %, to 20 %, preferably about 12 %.

The content of molybdenum oxide is 4 % to 20 %, preferably about 16 %.

The refractory oxides, introduced separately or simultaneously, have the following contents in the compounds:

Magnesia MgO: 10 % to 60 %, preferably 40 % to 50 %.

Silica SiO₂ : 0.2 % to 10 %, preferably about 8 %.

Zirconia ZrO₂ : 5 % to 50 %, preferably about 30 %.

complex catalysts with limited porosities according to the invention are prepared by sintering at high temperatures (1300°C or higher), thus forming solid solutions.

Prior to sintering, the components of the catalysts are uniformly mixed, then compressed at pressures in the 1,000-10,000 bar range.

Due to this special method of preparation, the various components of the compound are combined into solid solutions.

The catalytic compounds of the invention are notably suitable for the oxidation of ammonia on stationary beds. The results are especially satisfactory when a mixture of ammonia and air containing 5 to 14 % ammonia by volume is led, with very high volume rates (between 10,000 and 500,000 Nl/h per liter catalyst), under absolute pressure between 1 and 60 bars, with an initial temperature around 150°C, over a compound such as described above.

According to a variation of the method, the air in the mixture is enriched with oxygen.

The use of the said catalytic compounds in stationary beds makes it possible to use tubes with small diameters instead of the conventional reactors.

The mechanical strength and high hardness of the catalytic compounds make them especially valuable for the catalytic oxidation of ammonia on stationary beds.

The fluidized-bed method is carried out under pressures which can reach 60 bars. The reaction mixture is introduced into a compound according to the invention under the shape of particles with sizes between 60 and 250 μ, at temperatures between 500°C and 800°C, the volume rate on the fluidized bed being 3,500 to 20,000 Nl/h per liter catalyst. The amount of ammonia in the mixture is 5 to 14 % by volume. The air may be oxygen-enriched.

The following illustrative examples do not limit the scope of the invention.

EXAMPLE 1

A catalyst is prepared by intimately mixing the components, compressing the mixture to about 1,000 bars, then sintering at high temperature, between 1300°C and 1400°C, so as to get the following formulation by weight:

    Compound A :                                                                               NiO      8.5 %      ZrO.sub.2                                                                             31.7 %                                              MgO      49.5 %     V.sub.2 O.sub.5                                                                       0.9 %                                                SiO.sub.2                                                                              8.6 %      Pt     0.7 %                              

The specific surface area is 0.30 m² /g.

Catalyst A is charged into a tubular reactor with a heat exchanger allowing control of the temperature of the catalytic bed.

The NH₃ + air mixture is preheated to 150°C. At the outlet, the gases are converted to HNO₃, and the results are expressed as converted ammonia.

The results of this test on a stationary bed are shown on Table I hereafter.

                                      TABLE I                                      __________________________________________________________________________                           Temperature of gas mixture                               No.                                                                               VvH  NH.sub.3 /Pt                                                                        % NH.sub.3                                                                           P  IT  HT  OT   Yield                                                    by volume                                                                            bars                                                                              °C                                                                          °C                                                                          °C                                                                           %                                           __________________________________________________________________________     1  100,000                                                                              780 9.6   1  150 820 875  92                                          2  150,000                                                                             1,170                                                                               9.6   1  150 820 875  94                                          3  200,000                                                                             1,560                                                                               9.6   1  150 800 850  96                                          4  250,000                                                                             1,950                                                                               9.6   1  150 800 850  94                                          5  400,000                                                                             3,120                                                                               9.6   1  150 800 850  92                                          6  500,000                                                                             3,980                                                                               9.6   1  150 800 850  88                                          7  200,000                                                                             1,560                                                                               9.6   1  150 700 750  96                                          __________________________________________________________________________      No = N° test                                                            P = pressure                                                                   IT = inlet temperature                                                         HT = halfway temperature                                                       OT = outlet temperature.                                                 

The NH₃ /Pt ratio expresses the kg/h ammonia introduced per kg platinum in the catalyst.

VvH expresses volumetric speed = ratio of flow gaseous mixture NH₃ + air

NlH to volume of catalyst expressed in liter.

The yield is the percent ammonia converted to nitric acid.

As a comparative test, Table II hereafter shows the results obtained under the best practical conditions on platinum gauzes.

                                      TABLE II                                     __________________________________________________________________________                   Temperature of gas mixture                                                                  Temperature                                         NH.sub.3 /Pt                                                                        % NH.sub.3 by                                                                        P  Inlet   Outlet                                                                              of platinum                                              volume                                                                               bars                                                                              °C                                                                              °C                                                                           gauzes °C                                                                      Yield %                                      __________________________________________________________________________     133  9.6   1  130     790  840    96                                           __________________________________________________________________________

A parallel between test n° 7 on Table I and the test on Table II shows that catalytic compound A according to the invention makes it possible to treat, with the same amount of platinum, a flow rate 1,560/133 = 11.7 times higher than with conventional platinum screen gauzes.

On the other hand, the temperature is lower by about 100°C with the catalyst according to the invention than with conventional platinum gauzes.

EXAMPLE 2

A catalyst without platinum or metals of the platinum group is prepared by mixing and shaping the components, then by sintering at 1300°C or higher, so as to obtain the following formulation:Compound B : NiO 7.9 % V₂ O₅ 1.0 % MgO 45.0 % ZrO₂ 29.2 % SiO₂ 8.0 % Fe₃ O₄ 7.9 %

Compound B is tested in the same reactor as in Ex. 1. The results of this stationary bed test are summarized on Table III.

                                      TABLE III                                    __________________________________________________________________________                      Temperature of gas mixture                                    No.                                                                               vol/vol/h                                                                           % NH.sub.3 by                                                                        P  IT  HT  OT   Yield                                                    volume                                                                               bars                                                                              °C                                                                          °C                                                                          °C                                                                           %                                                __________________________________________________________________________     1   50,000                                                                             0.6   1  150 800 850  84                                               2  100,000                                                                             9.6   1  150 800 850  84                                               3  150,000                                                                             9.6   1  150 800 850  80                                               4  200,000                                                                             9.6   1  150 800 850  70                                               5   10,000                                                                             9.6   1  150 800 850  94                                               __________________________________________________________________________

EXAMPLE 3

Catalytic compound C is prepared under the same conditions as in Ex. 1 and Ex. 2.

    ______________________________________                                         Compound C :                                                                                  CoO          12 %                                                              V.sub.2 O.sub.5                                                                             1.0 %                                                             MgO          42.1 %                                                            ZrO.sub.2    29 %                                                              SiO.sub.2    8 %                                                               Fe.sub.3 O.sub.4                                                                            7.9 %                                              ______________________________________                                    

Compound C is tested in the same way as in Ex. 1.

Table IV hereafter summarizes the conditions and results of the test.

                                      TABLE IV                                     __________________________________________________________________________                      Temperature of gas mixture                                    No.                                                                               VvH  % NH.sub.3 by                                                                        P  IT  HT  OT   Yield                                                    volume                                                                               bars                                                                              °C                                                                          °C                                                                          °C                                                                           %                                                __________________________________________________________________________     1   50,000                                                                             9.6   1  150 750 800  86                                               2  100,000                                                                             9.6   1  150 750 800  86                                               3  150,000                                                                             9.6   1  150 750 800  84                                               4  200,000                                                                             9.6   1  150 750 800  72                                               5   10,000                                                                             9.6   1  150 750 800  94                                               __________________________________________________________________________

EXAMPLE 4

This example is given as a comparative test.

The catalyst is prepared differently from Ex. 1.

Alumina is impregnated with a solution of tetrachloroplatinic acid in such a way that after treatment at 900°C, there remains 2 % platinum deposited on the carrier. The specific surface area of the catalyst is 86.5 m2/g; the average diameter of the pores is 92 A.

Catalyst D of this example is tested under the same conditions as in Ex. 1. The results are shown on Table V hereafter.

                                      TABLE V                                      __________________________________________________________________________                      Temperature of gas mixture                                    No.                                                                               % NH.sub.3 by                                                                       VvH   P  IT  HT  OT   Yield                                               volume     bars                                                                              °C                                                                          °C                                                                          °C                                                                           %                                                __________________________________________________________________________     1  9.6  100,000                                                                              1  150 820 832  34                                               2  9.6  150,000                                                                              1  150 835 845  32                                               3  9.6  200,000                                                                              1  150 800 821  28                                               4  9.6  250,000                                                                              1  150 830 835  24                                               5  9.6  300,000                                                                              1  150 910 900  28                                               6  9.6  300,000                                                                              1  150 875 856  24                                               __________________________________________________________________________

A parallel with the results of the tests in Ex. 1 shows the comparatively low yields obtained in this test.

The high platinum content of catalyst D (2 % instead of 0.7 % for catalytic compound A) clearly shows that platinum is not the only active element in the catalysis of the oxidation reaction of ammonia.

EXAMPLE 5

Into a fluid-bed reactor is introduced catalytic compound A of Ex. 1, previously screened to the proper particle size to allow fluidization at the flow rate of the NH₃ + air gas mixture. The reactor includes a heat exchanger for evacuating the calories from the reaction.

The results of the test are shown on Table VI hereafter.

                  TABLE VI                                                         ______________________________________                                                                       Temperature of                                   No.   VvH      % NH.sub.3 by                                                                            P    fluidized bed,                                                                           Yield                                                 volume    bars °C %                                      ______________________________________                                         1      3,500   9.6       1    750       71                                     2      5,000   9.6       1    750       73                                     3      7,450   9.6       1    750       82                                     4     10,000   9.6       1    750       92                                     5     12,000   9.6       1    750       95                                     6     17,000   9.6       1    750       96                                     7     20,000   9.6       1    750       96                                     ______________________________________                                    

FIG. 1 of the appended drawing shows the yield of ammonia vs. the volume rate (vol/vol/h). The volume rates (abscissae) are in Nl/h, the yields (ordinates) in %.

It should be noticed that the yields reach highly desirable values from volume rates of 10,000 Nl/h upwards.

EXAMPLE 6

Comparative tests on fluidized beds with catalytic compound A according to the invention and with catalyst D of Ex. 4. The tests were conducted in the fluidizing reactor of Ex. 5, the volume rate being 15,000 Nl/h in all tests, the NH₃ volume percentage being 9.6 in every case and the pressure in the reactor 1 bar.

The comparative yield (% of NH₃ converted) according to the temperature of the fluidized bed are shown on Table VII hereafter, and on curves A and D of FIG. 2 of the appended drawing; the yields (ordinates) are in % NH₃ and the temperatures (abscissae) in °C.

                  TABLE VII                                                        ______________________________________                                         Compound A         Compound D                                                  No.  Temperature of                                                                               Yield   Temperature Yield                                        fluidized bed °C                                                                      %       fluidized bed °C                                                                    %                                       ______________________________________                                         I    525           75      528         43                                      2    565           85      560         48                                      3    630           87      610         54                                      4    670           93      640         50                                      5    780           94      700         55                                      ______________________________________                                    

The parallel clearly shows the superiority of compound A according to the invention over a catalyst with high platinum content deposited as a continuous layer on an inert carrier, in the case of a fluidized bed.

EXAMPLE 7

In this example, the behavior of the catalyst in a stationary bed is investigated under various pressures, the yields being expressed as % NH₃ converted.

In the following series of tests, the results of which are shown on Table VIII, the volume % NH₃ is 9.6, the volume rate is 200,000 Nl/h, and the temperature is controlled in the same way, the outlet temperature being 875°C.

                  TABLE VIII                                                       ______________________________________                                         Pressure             Yield                                                     bars                 %                                                         ______________________________________                                          1                   96                                                        10                   95                                                        25                   95                                                        40                   88                                                        ______________________________________                                    

Curve 3 on FIG. 3 of the appended drawing shows the effect of pressure on yield. The pressures (abscissae) are in bars and the yields (ordinates) are expressed as % NH₃ converted.

The outstanding behavior of the catalyst should be noted. This type of catalyst is very valuable, as it allows the use of a stationary bed of catalyst along a tube with a small diameter which can withstand high pressures.

EXAMPLE 8

In this example, the tests are made on the fluidized bed of Ex. 5 under various pressures with catalytic compound A.

The conditions are as follows:

% NH₃ by volume: 9.6

vol/vol/h = 20,000 Nl/h.

Temperature of fluidized bed: 750°C

The results are summarized on table IX hereafter:

                  TABLE IX                                                         ______________________________________                                         Pressure bars         Yield %                                                  ______________________________________                                          1                     96                                                      20                     95                                                      35                     93                                                      48                     91                                                      60                     98                                                      ______________________________________                                    

The outstanding behavior of the catalyst should be noticed. The yields (as % NH₃ converted) are quite attractive, even under high pressures.

These results are shown on curve 3, FIG. 4 of the appended drawing, on which the yields are the ordinates and the pressures are the abscissae.

EXAMPLE 9

Catalytic compound E is prepared under the same conditions as in Example 1 and Example 2.

    ______________________________________                                         Compound E:                                                                                 Bi.sub.2 O.sub.3                                                                          10 %                                                                V.sub.2 O.sub.5                                                                           1 %                                                                 MgO        42.1 %                                                              ZrO.sub.2  29 %                                                                SiO.sub.2  8 %                                                                 Fe.sub.3 O.sub.4                                                                          9.9 %                                                  ______________________________________                                    

Compound E is tested in the same way as in Example 1.

Table X hereafter summarizes the conditions and results of the test.

                                      TABLE X                                      __________________________________________________________________________                      Temperature of gas mixture                                    No.                                                                               VvH  % NH.sub.3 by                                                                        P  IT  HT  OT   Yield                                                    volume                                                                               bars                                                                              °C                                                                          °C                                                                          °C                                                                           %                                                __________________________________________________________________________     1   50,000                                                                             9.6   1  150 750 800  96                                               2  100,000                                                                             9.6   1  150 750 800  94                                               3  150,000                                                                             9.6   1  150 750 800  94                                               4  200,000                                                                             9.6   1  150 750 800  90                                               5   10,000                                                                             9.6   1  150 750 800  90                                               __________________________________________________________________________ 

What we claim is:
 1. In a method for the catalytic oxidation of ammonia comprising passing a mixture of ammonia and air over a catalyst under ammonia oxidation conditions, the improvement wherein said catalyst comprises:a composition of limited porosity, with a specific surface area between 0.02 and 2m² /g, wherein said composition consists essentially of 0.1-10% of an active material selected from the group consisting of the metals of the platinum group, and a refractory oxide carrier comprising, in the composition, 10-60% magnesia, 0.2 to 10% silica and 5-50% zirconia, all combined by mixing said active material and said carrier in powdered form, compressing at 1,000-10,000 bars pressure and sintering at 1300° C. or higher.
 2. A method in accordance with claim 1 wherein said conditions comprise a flow rate of ammonia and air between 10,000 and 500,000 Nl/h. per liter catalyst under pressures lying between 1 bar and 60 bars, with an inlet temperature around 150°C.
 3. A method for the catalytic oxidation of ammonia acording to claim 1 in which the mixture of ammonia and air contains 5 to 14% ammonia by volume.
 4. A method for the catalytic oxidation of ammonia according to claim 1, in which the mixture is ammonia and air enriched with oxygen.
 5. A method according to claim 1, wherein the content of metal of the platinum group is from 0.5 to 4%.
 6. A method in accordance with claim 1 wherein said refractory material comprises 40-50% magnesia, about 8% silica, and about 30% zirconia.
 7. In a method for the catalytic oxidation of ammonia comprising passing a mixture of ammonia and air over a catalyst under ammonia oxidation conditions, the improvement wherein said catalyst comprises:a composition of limited porosity, with a specific surface area between 0.02 and 2m² /g, wherein said composition consists essentially of 0.1-10% of an active material selected from the group consisting of the metals of the platinum group, a refractory oxide carrier comprising, in the composition, 10-60% magnesia, 0.2 to 10% silica and 5-50% zirconia, and at least one metal oxide of the group consisting of oxides of iron, nickel, cobalt, titanium, vanadium, bismuth and molybdenum, all combined by mixing said active material, said refractory oxide carrier and said metal oxide in powdered form, compressing at 1,000-10,000 bars pressure and sintering at 1,300°C or higher.
 8. A method in accordance with claim 7 wherein said refractory material comprises 40-50% magnesia, about 8% silica, and about 30% zirconia.
 9. A method according to claim 8, wherein the said at least one metal oxide is selected from the group consisting of oxides of iron present in an amount of 0.5 to 20% for Fe₃ O₄, and 9 to 80% for Fe₂ O₃, of nickel present in an amount of 4 to 20% for NiO, of bismuth present in an amount of 4 to 20%, of molybdenbum present in the amount of 4 to 20%, of cobalt present in the amount of 4 to 20% for CoO, and of vanadium present in the amount of 0.5 to 10% for V₂ O₅.
 10. A method in accordance with claim 8 wherein said refractory material comprises 40-50% magnesia, about 8% silica, and about 30% zirconia.
 11. In a method for the catalytic oxidation of ammonia in a fluidized bed comprising introducing a mixture of ammonia and air into a fluidized bed of catalyst under ammonia oxidation conditions, the improvement wherein said catalyst comprises:a composition of limited porosity, with a specific surface area between 0.02 and 2m² /g, wherein said composition consists essentially of 0.1-10% of an active material selected from the group consisting of the metals of the platinum group, and a refractory oxide carrier comprising in the composition, 10-60% magnesia, 0.2 to 10% silica and 5-50% zirconia, all combined by mixing said active material and said carrier in powdered form, compressing at 1,000-10,000 bars pressure and sintering at 1,300°C. or higher.
 12. A method in accordance with claim 11, wherein said conditions comprise a flow rate of ammonia and air between 3,500 and 20,000 Nl/h per liter catalyst, under pressure lying between 1 and 60 bars and at temperatures between 500° and 800° C.
 13. A method in accordance with claim 11, wherein the mixture of ammonia and air contains 5-14% ammonia by volume.
 14. A method in accordance with claim 12, wherein the mixture of ammonia and air is enriched with oxygen.
 15. A method in accordance with claim 11, wherein the content of metal of the platinum group is from 0.5 to 4%.
 16. A method in accordance with claim 11, wherein said refractory material comprises 10-60% magnesia, 0.2-10% silica and 5-50% zirconia.
 17. A method in accordance with claim 11, wherein said refractory material comprises 40-50% magnesia, about 8% silica and about 30% zirconia.
 18. A method according to claim 17 wherein the said at least one metal oxide is selected from the group consisting of oxides of iron present in an amount of 0.5 to 20% for Fe₃ O₄ and 9 to 80% for Fe₂ O₃, of nickel present in an amount of 4 to 20% for NiO, of bismuth present in an amount of 4-20%, of molybdenum present in the amount of 4-20%, of cobalt present in the amount of 4 to 20% for CoO, and of vanadium present in the amount of 0.5 to 10% for V₂ O₅.
 19. In a method for the catalytic oxidation of ammonia in a fluidized bed comprising introducing a mixture of ammonia and air into a fluidized bed of catalyst under ammonia oxidation conditions, the improvement wherein said catalyst comprises:a composition of limited porosity, with a specific surface area sintering 0.02 and 2m² /g, wherein said composition consists essentially of 0.1-10% of an active material selected from the group consisting of the metals of the platinum group, a refractory oxide carrier comprising, in the composition, 10-60% magnesia, 0.2 to 10% silica and 5-50% zirconia, and at least one metal oxide of the group consisting of oxides of iron, nickel, cobalt, titanium, vanadium, bismuth and molybdenum, all combined by mixing said active material, said refractory oxide carrier and said metal oxide in powdered form, compressing at 1,000-10,000 bars pressure and sntering at 1,300°C or higher. 